Articles producció científica> Química Física i Inorgànica

Backbone flexibility of extended metal atom chains. Ab initio molecular dynamics for Cr3(dpa)4X2 (X = NCS, CN, NO3) in gas and crystalline phases 

  • Identification data

    Identifier: PC:3130
    Authors:
    López, J.Spinak, M.Arcisauskaite, V.De Graaf, C.
    Abstract:
    Filiació URV: SI
  • Others:

    Author, as appears in the article.: López, J. ; Spinak, M. ; Arcisauskaite, V. ; De Graaf, C.
    Department: Química Física i Inorgànica
    URV's Author/s: LÓPEZ FERNÁNDEZ, JAVIER; Spinak, M. ; Arcisauskaite, V. ; DE GRAAF , CORNELIS
    Keywords: metal atom chains Ab initio
    Abstract: Recently published static DFT and CASSCF/CASPT2 calculations depicted extremely flat Potential Energy Surfaces (PESs) for the Cr¿Cr flexibility of Cr3(dpa)4X2 (X = NCS¿, CN¿, NO3¿) extended metal atom chains (EMACs) (M. Spivak, et al., Dalton Trans., 2017, 46, 6202). We herein explore the thermal and crystal packing effects on the structure of EMACs using ab initio molecular dynamics (MD). Car-Parrinello DFT-based simulations of the isolated molecules show that thermal energy favors asymmetric arrangements of the Cr3 chain due, in part, to the bending of the axial ligands (X) and the increased X¿Cr distance, both of which weaken X ¿ Cr ¿-donation. This effect is even more prominent in the crystalline phase due to the interaction between the axial ligands of neighboring molecules in the unit cell. This could explain the typical discrepancies between the experimental and theoretical characterization of Cr3 EMACs observed in the literature
    Research group: Química Quàntica
    Thematic Areas: Chemistry Química Química
    licence for use: https://creativecommons.org/licenses/by/3.0/es/
    ISSN: 1477-9226
    Author identifier: 0000-0003-0322-6796; ; ; 0000-0001-8114-6658
    Record's date: 2018-02-28
    Last page: 15493
    Journal volume: 46
    Papper version: info:eu-repo/semantics/acceptedVersion
    Link to the original source: http://pubs.rsc.org/en/Content/ArticleLanding/2017/DT/C7DT03520A#!divAbstract
    Funding program: altres; EPSRC; EP/K021435/1 european; COST Ac- tion ECOSTBio; CM1305 altres; Xarxa d¿R+D+I en Química Teòrica i Computacional; XRQTC altres; Grupos Consolidados; 2014SGR199 plan; Excelencia; CTQ2014-51938-P
    Licence document URL: https://repositori.urv.cat/ca/proteccio-de-dades/
    Article's DOI: 10.1039/c7dt03520a
    Entity: Universitat Rovira i Virgili
    Journal publication year: 2017
    First page: 15487
    Publication Type: Article Artículo Article
  • Keywords:

    Dinàmica molecular
    metal atom chains
    Ab initio
    Chemistry
    Química
    Química
    1477-9226
  • Documents:

  • Cerca a google

    Search to google scholar